Natural Assembly of Electroactive Metallopolymers on the Electrode Surface: Enhanced Electrocatalytic Production of Hydrogen by [2Fe-2S] Metallopolymers in Neutral Water.

A molecular catalyst attached to an electrode surface can offer the advantages of both homogeneous and heterogeneous catalysis. Unfortunately, some molecular catalysts constrained to a surface lose much or all of their solution performance. In contrast, we found that when a small molecule [2Fe-2S] catalyst is incorporated into metallopolymers of the form PDMAEMA--[2Fe-2S] (PDMAEMA = poly(2-dimethylamino)ethyl methacrylate) and adsorbed to the surface, the observed rate of hydrogen production increases to > 10 s per active site with lower overpotential, increased lifetime, and tolerance to oxygen.